Azo-dyestuffs insoluble in water



Patented Aug. 23, 1960 thee AZO-DYESTUFFS INSOLUBLE 1N WATER HerbertKracker and Hans Albert, Offenbach (Main),

Germany, assignors to Farbwerke Hoechst Aktiengesellschaft vormalsMeister Lucius & Briining, Frankfurt am Main, Germany, a corporation ofGermany No Drawing. Filed Oct. 14, 1958, Ser. No. 767,096

Claims priority, application Germany Oct. 19, 1957 6 Claims. (Cl.260-188) The present invention relates to new azo-dyestulfs insoluble inwater and to a process for preparing the same; more particularly itrelates to dyestufis corresponding to the following general formula:

wherein R represents an aromatic radical.

We have found that azo-dyestuffs insoluble in water having valuableproperties are obtained by coupling in substance, on the fiber or onanother substratum the diazonium compound from an ortho-amino-azocompound of the general formula O.a1kyl l QN=NO .alkyl S Og.aryl NH;

with an arylamide of 2,3-hyroxynaphthoic acid which is free from groupsimparting solubility in Water.

The new dyestuffs yield on vegetable fibers, including fibers fromregenerated cellulose, according to known dyeing and printing methods,mainly greenish brown to green dyeings and prints of good fastnessproperties.

The dyestuffs can also be prepared in substance or on a substratum andmay be used for coloring high mo EXAMPLE 1 Cotton fabric is padded onthe foulard with the following solution and dried:

12 grams of 2,3-hydroxynaphthoylaminobenzene are pasted with 20 grams ofMonopol Brilliant oil, and

18 cc. of sodium hydroxide solution of 38 Be. and the whole is made upto 1 liter with boiling Water.

The dried fabric is printed with a printing paste containing, perkilogram, diethoxy-2'-phenylsulfonyl-4-nitro-1,1'-azobenzene in the 10.7grams of 2-amino-4,5-

form of a diazonium compound prepared in the usual manner, 1 gram of areaction product from about 20 mols of ethylene oxide and 1 mol ofoctodecyl alcohol, 20 cc. of acetic acid of 50% strength, and tragacanthas thickening agent.

The fabric is then dried, washed with hot dilute sodium carbonatesolution, rinsed, soaped for 10 minutes at 95 C. with a solutioncontaining, per liter of water, 1 gram of a reaction product from about10 moles of ethylene oxide and 1 mol of isododecyl phenol, andfurthermore 3 grams of sodium carbonate, rinsed again and dried. A dullgreen print is obtained.

When in the above example 2-amino-4,S-di-n-propoxy-2'-phenylsulfonyl-4-nitro-1,1-azobenzene is used instead of 2amino-4,5-diethoxy-2-phenylsulfonyl-4'-nitro-1,1- azobenzene, a similarprint is obtained.

EXAMPLE 2 Cotton fabric is padded on the foulard with the followingsolution and dried:

16.2 grams of 1 (2',3' hydroxynaphthoylamino) 2,4-

dimethoxy-S-chlorobenzene are pasted with 20 grams of Monopol Brilliantoil,

14 cc. of sodium hydroxide solution of 38 B., and

100 cc. of water, boiled and the whole is made up to 1 liter with watercontaining per liter 5 grams of Monopol Brilliant oil and 2 cc. ofsodium hydroxide solution of 38 Be.

The dried fabric is developed on the foulard with a solution containing,per liter of water, 10.7 grams of 2-arnino-4,5-diethoxy 2phenylstdfonyl-4-nitro-1,1'- azobenzene in the form of a diazoniumcompound prepared in the usual manner, 1 gram of a reaction product fromabout 20 mols of ethylene oxide and 1 mol of octodecyl alcohol and 20cc. of acetic acid of 50% strength.

After an air passage for about 30 seconds, the material is rinsed first,for 10 seconds at -90" C. It is then rinsed in the cold and soaped forl0-20 minutes at C. with a solution containing, per liter of water, 1gram of a reaction product from about 10 mols of ethylene oxide and 1mol of isododecylphenol, and furthermore 3 grams of sodium carbonate,rinsed again and dried. A yellowish green of good fastness properties isobtained.

EXAMPLE 3 Cotton yarn on cross-wound bobbins is treated in a closedapparatus for 45 minutes at 35 C. in a goods-toliquor ratio of 1:15 inthe following impregnation bath, rinsed with a solution containing, perliter of water, 20 grams of sodium chloride and 1 cc. of sodiumhydroxide solution of 38 34%., and developed at 15 C. in the developingbath described below. The material is then soaped in the usual mannerrinsed and dried.

Impregnation bath 9.6 grams of1-(2,3'-hydroxynaphthoyla1nino)-2-methoxy-4-chloro-5-methylbenzene aredissolved in 16 cc. of denatured alcohol,

3.2 cc. of a sodium hydroxide solution of 38 B.,

12 cc. of water, and

4.8 cc. of a formaldehyde solution of 33% strength and the Whole is madeup to 8 liters with Water of 35 C.

24 grams of a condensation product from high molecular fatty acids andprotein degradation products, and

80 cc. of sodium hydroxide solution of 38 B.

Developing bath 9.5 grams of 2-amino-4,5-diethoxy-2-phenylsulfonyl-4'-nitro-l,1'-azobeuzene in the form of a diazo'nium compound prepared inthe usual manner are dissolved in 8 liters of water containing 8 gramsof a reaction product from about 20 mols of Q- t. V 3 4 ethylene oxideand 1 mol of octodecyl alcohol, and wherein X represents a lower alkylgroup and R'repre- 40 cc. of acetic acid of 50% strength. sents a memberselected from the group consistin of A yellowish green dyeing of oodfastness properties is Phenyl, yrg y yp y dimethoxyphenyl, methylphenyl,dimethylphenyl, methyl-methoxyphenyl,

ed. Qbtam EXAMPLE 4 5 rnfithyl-chlorophenyl, dimethoxy-chlorophenyl,methoxyc oro-methylphenyl, nitrophenyl and naphthyl. grams of q-'pheliylsulionyl'4 2. The azd-dyestufi which corresponds to thefollown1tro-1,1-azo-benzene 1n the form of the dlazonium suling formula,V fate are dissolved in'4 liters of water. Into this diazo solution isrun, while stirring well, a solution'of 30 grams of OCH 1(2,3'-hydroxynaphthoylamino)-2-methoxybenzene in I 3 dilutesodiumhydroxide solution. The coupling is com- 0 OCH pleted by graduallyheating to 90 C. The greenishrblack T dyestuif so obtained is filtered01f, washed well and dried. so n 7 N The coupling can also be carriedout in the presence 1 g 5 V H I of a substratum adapted for thepreparation of color' V IN V lakes.

The following table indicates a number of further on (13cm componentswhich can be used in this invention, and also 7 the tints of theazo-dyestufls produced fiom these components on the fiber, whichlikewise possess good fast- CH ness properties.

Diazo component Coupling component Tint 2 amino 4,5 diethoxy 2phenylsulfonyl 1 (2,3 -hydroxynaphthoyl amino)- dull green.

4-nitro-1,l-azobenzene V 1 1 -methoxybenzene Do 1(2,3-l1ydroxynaphthoy1-amlno) -2, covered green.

4-dimethylbenzene Do 1 (2,3 -hydr oxynaphthoyl amino) dull green.

. 2-methyl-4-methoxy-benzene Do l (2,3 -hydroxynaphthoy1- amino) coveredyellowish 2,5-dimethoxybenzene green. Do 2 (2' ,3 hydroxynaphthoylamino) dull grey-green.

naphthalene 1.- (2,3 hydroxynaphthoyl-amino) yellowish green.

2,5-dlmethoxy-4-chlorobenzene 1 (2,3' -hydroxynaphthoylamino) coveredyellowish 1 (2,3 -hydroxynaphthoyl amino) dull green.

4-ethoxybenzene 1 (2,3"- hydroxynaphthoyl amino) covered green.

2,3-dimethylbenzene 1 (2,3 hydroxynaphthoyl amino) brownish green. 12-methoxybenzene 2 amino- 4,5 dunethoxy 2 phenylsulionyl- 1 (2,3hydroxynaphthoyl amino) covered green.

4-nitro-1,1-azobenzene 2-methyl-4-methoxy-benzene Do l (2 ,3hydroxynaphthoyl amino) yellowish brown.

4-methoxybenzene I 1 (2,3 hydroxynaphthoyl amino) grey brown.

4-ethoxybenzene 7 1 (2,8 -hydroxynaphthoyl amino) covered yellowish2,4-dimethoxy-5-chlorobenzene green. 1 (2,3' hydroxynaphthoyl amino) Do.

2,5 dlmethoxy4-chlorobenzene 1 (2,3 hydroxynaphthoyl amino) coveredgreen 2,3-dhnethy1benzene l (2,3 hydroxynaphthoyl amino) coveredyellowish e 2,5-dlrnethoxybenzene green. Do2,3-hydroxynaphthoyl-amlnobenzene. brownish green. Do 1 (2,3hydroxynaphthoyl amino) Do.

2-methyl-4-ehlorobenzene Obviously many modificationsand variations ofthe present invention are po'ssible in the light of the above teachings.It is, therefore, to be understood that within 3. The azohyeswfi' whichcon-espgnds t0 the f llo the scope of the appended claims the inventionmay be ihg f l practiced otherwise than as specifically described.

We claim: v v V 1. Azo-dyestufis insoluble in water which correspond 0OH to the following general formula: V 3 OX I oiN N=N OOH:

OzN' N=N OX 502.0011! II? SO2-C6H5 1T1 N v V N V i i 7 0 5; 1011i on V VV 1 CO-NH c1 V V 7 CH:

4. The azo-dyestuff which corresponds to the follow- 6. The azodyestufiwhich corresponds to the followiug formula: ing formula:

3cm 002m omQrr: 000B; 5 OzNQN=NOOCnHs somam I11 Somali, 1: |I

on OH :1 CO-NHQO CH; 0 O-NH 0cm Ha CE:

5. The azo-dyestufi which corresponds to the follow- 15 ing formula:References Cited in the file of this patent 001m UNITED STATES PATENTS I2,105,919 Hofia et a1. Jan. 18, 1938 O2NQN=N -O 02H;

sol-USES 1L5 on c cam- 001!

1. AZO-DYESTUFFS INSOLUBLE IN WATER WHICH CORRESPOND TO THE FOLLOWINGGENERAL FORMULA: